Liquid coating composition



' Oil varnishes are comprised of a drying oil and I requirement. I

I have found'that a highly desirable oil varnish can be obtained by incorporating into a dry- Patented ;Apr. 17., 1945 PATENT orries 2,373,866 LIQUID COATING coMPos 'rIoN 'Alger L. were, BemOynwyd, Pa., assiznor. to J The United Gas Improvement Company, a corporation of Pennsylvania" 'No Drawing. Application November 19, 1942,

Serial No. 466,223

' 14 Claims. (01. 260-23) This application is a continuation-in-part of my copending application Serial No. 264,593, flied March28,1939.-

This invention pertains generally to liquid coating} compositions, and pertains particularly to varnishes having incorporated therein synthetic hydrocarbon resins. v I

There are two principal types of varnishes, spirit varnishes and oil varnishes. Spirit varnishes are solutions of resins and/or plastics in volatile solvents. I Drying of spirit varnishes accomplished by the evaporation of the solvent,

surface to which the varnish has been applied.

a resin, and both the drying oil and the resin form a film upon the surface to which the varnish ha been applied, The drying oil imparts toughness and elasticity to the film, and-the resin renders the film hard and glossy. This invention is particularly concernediwith drying oil varnishes.

Because of the greg demand of the varnish industry for more durabl and quick drying finishes, synthetic resin have, in many cases, replaced the natural resins which were formerly employed entirely in the production 01' oil varnishes. I

In order to be suitable for use in an oil varnish,

with the oils employed in the preparationflof found to be Sunsuitable for use in the preparation of oil varnishes, because they-fail to meet this ing oil a resin obtainable by the catalytic polymerization of a more or less narrow crude tractained; as the result of cracking oil in gas manufacture. (a

As disclosed in my above mentioned copending application, in the high temperature cracking of petroleum oils, for example, in the manufacture of oil gas or carburetted water gas, there is formed a complex mixture of hydrocarbons from which liquid constituents. maybe obtained by mixture of hydrocarbons obtained by, condensation at atmospheric temperature. Upon distillation of the tar or of light oil derived therefrom, a portion is recovered which 1 unsaturated hydrocarbons.

are more useful and accurate than the end boi1-- I able. 40' tion separated from the hydrocarbon mixture obv resin changes very rapidly.

sists largely of aromatic hydrocarbons such as benzene, toluene and the xylenes. 1

Another portion boiling between about 140 C. and 190 C. contains, in addition to large quantitles of higherai'omatics, a relatively large percentage of a considerable number. of different The light oil from which these cuts are derived is-fundamentally different from the light oil or solvent'naphtha derived from coal tar in that this material contains no more than traces of any/oxygen containing bodies, whereas coal tar leavlng fil f the resin deposited upon the 'light'oil contains relatively large quantities of oxygen containing compounds of which couma- [l rone is a well known example.

V I have discovered that a new and useful resin= product suitable for incorporation into a drying oil for the production of varnishes can be obtained uponthe catalytic polymerization of a more or less narrow crudefraction'separated 'from the hydrocarbon mixtures obtained as the result of cracking oil in gas manufacture.

rial will considerably raise theend ,boilin'g'point,

and Iurthersince it is 'diflicult to obtain an end boiling point because ofthe likelihood of polymeri'zing the last few percent of the unsaturated a synthetic resin should be highly, compatible matefial' I preferrto define my crude fractions in terms of intermediateboiling points or boiling ranges. I

- For this purpose the 5% and 10% boiling points are more useful and accurate than the initial boiling point, and-the and boiling points ing point. When distillingat atmospheric pressure even the 90% boiling point may be unreli I find, for instance, that when the 5% boil-ing point is approximately 167.2".'C., or above, and

' when the 90% boiling point is approximately 174.6 C., or below, that a'highly useful resin product may be obtained upon polymerization.

On the other hand, when the 5% boiling point is much below 167.2? C., or the 90% boiling point.

or the is much above 114.6 C., the character Expressed;in terms of the 10% boiling point .and the 80% boiling point which are,-the more :In describing my crude fractionatherefore, it

might-be said that a preponderate portion boils boils between about 75 .C. and C. and'con- ,ll between'lfi'l' C. and 174.6 C.

boron trifluoride-toluene complex.

, in the varnishes by agitation for 2 hours.

catalytically polymerize it preferably using a datalyst of the metallic halide type or a complex'thereof, for example, a boron trifiuoride-organic solvent complex, such as'boron trifiuoride-diethyl .ether complex, boron trifluoride-dimethyl ether .complex, borontrifluoride-phenyl ethyl ether complex, boron trifluoride-phenyl methyl ether complex, boron trifluoride-dioxan complex, and The ether complexes are especially suitable. Boron halides are grouped with the metallic halides because of 4 their similarity of action.

Other examples of complex catalysts are the aluminum chloride-organic solvent complexes.

Accordingly, the metallic halides. which are preferably employed in the preparation of the resins employed in the varnishes of this invention are characterized by the fact that they are capable of hydrolyzing in the presence of water to give an acid reaction. They may for convenience be designated therefore as acid-acting metallic halides; The preparation ofcomplexes of this character, in general, comprises adding the halide to the solvent with agitation. If a reaction takes place, which depends upon the solvent chosen, a definite chemical compound is formed which comprises the complex.

Complex catalysts may be employed in the form of suspensions, emulsions or solution in organic 1 solvents ofwhich benzene, toluene,- and solvent f v naphtha are examples. Such suspensions, emnlv sions, or solutions are formed by adding the catalystto the solvent followed by stirring. As an example I find that a concentration of complex in toluene of 1% by weight of toluene is very-suitable'as a catalyst suspension, although any other concentration or solvent suitable for the purpose may be employed.

The crude fraction may be employed in the form of a solution in a suitable solvent of which benzene, toluene and solvent naphtha are examples.

The following specific example will serve to illustrate' a methodby which resins suitable for use pared. v

. I EXAMPLE 1 A 1000 grams portion of a crude fraction falling within my specifications and contain'ing;66% ofunsaturates, as determined bythe well known bromine titration method, was'diluted with 500- grams of commercial toluene. This diluted ma.-.

terial was added to 1000 grams of commercial toluene containing cubic centimeters of boron trifluoride diethyl ether complex insuspension. 1 The addition-was made over 'a period of one hour with constant agitation.

Agitation wascontinued for a period of 6 2 hours to allow sufllcient time for the reaction to become complete. I

During the additionof thematerials and during the subsequent agitation, the temperature was for neutralizationand drying. This was followed .At the end of the 2 hour period a small amount of a filter aid, such as fullers earth or diatomaceous earth was added and the solution filtered.

Th flltrat'was subiectedtosteam distillation of. this invention may be preand the yield of dry polymer was 513 grams. This was equivalent to 51.3% of the weight of the crude fraction used as starting material or 77.7% of the total unsaturated hydrocarbons present.

As above indicated, the properties of resins prepared in this manner vary widely with the inclusion of substantial quantities of materials'boil- 'ing above or below the preferred boiling ranges set forth above.

This is clearly shown in the following table wherein is set forth boiling range data and polymerization resultsfor five different samples.

. TABLE 1 Boiling range of crude light oil fractions in C.

Sam- Sam- Sam- Sam- Sample 1 pie 2 pie 3 ple 4 pie 5 166- 0 168. 4 160. 5 168.6 167. 2 160. 2 170:9 171.2 167. 4 169. 4 171.0 171. 8 167. 7 169. 6 171.3 172.2 168.0 169. 7 171. 7 172. 5 168. 2 109.- 8 171. 9 172. 8 168. 4 169. 9 172. 1 173. 1 168.6 170.0 172. 4 173. 4 168. 9, 170. 3 152. 7 173. 7 169. 3 171.0 173. 2 174. 3 172. 9 174. 6 176. 5 5% l Dry or decomposed 174. 3 178. 3 184.3 187. 3 186. 0 .Density, d /4 0.8909 0. 8908 0. 8933 0. 8996 0. 9051 Re[ract1ve index12 20/D 1. 51-81 1.5200 1.5252 1. 5246 1.5250 Unsatm'ation by bromine titration in per cent 48.2 52.3 01.6 55.4 57.1

Results upon polymerization Sam- Sam- Sam- Sam Sample 1 ple 2 pie 3 pie 4 pie 5 Yield in per cent of starting material 28. 5 I 35. 8 54. 49. 7 47. 6 40 Yield in per cent 01' unsaturation 59. 4 67.4 88.2 89. 7 83. 4 Color, Gardner scale. 13. 5 8.8 5. 0 4. 5 9. 5 Softening goint by A. S.

T. M. all and ring method, "0 74. 8 88.2 95. 0 104. 8 127. 4 Solubility in grams per 1 100 grams of solvent: i

i E er 100 100 100 100 100 Acetone. 100 100 100 100 100 Toluene 100 100 100 100 100 High flash petroleum.

naphtha '100 100 100 100 100 Ethyl alcohol (95%). 1. 93 0. 42 0. 61 0. 49 0. 69 50 I Isoamy1a1cohol 14. 5 5.0 i 1. 56 0. 67 1.02

' It will be noted that the 5% boiling point of sample 2 is 167.2 C., that the 10% boiling point is 167.4- C., and that the lower portion of this sample is, therefore, satisfactory. The corresponding boiling'points of sample 1 are at least one degree lower and, therefore, unsatisfactory. It will also be noted that the 80% boiling point of sample 4 is 173.2 C., that the 90% boiling point is 174.6" C., and that the upper portion of this sample is therefore, satisfactory. The

It will also be noted that the 5% and 10% boiling points respectively of samples 3, 4, and 5 are higher than the corresponding boiling points of sample 2. Therefore, the lower portions of samples 3, 4, and 5 are satisfactory. Alsothe and boiling points (the latter .if taken) of samples '1, 2, .and 3 are lower than theccrresponding boiling points 'of sample 4.. Therefore, the upper portions of samples 1, 2, and 3 are satisfactory. However, overall samples '1 and 5 are preferably excluded, the former because of its 1 lower end and the latter because of its higherv 1 end. On the other hand. if the unpreferred upcorresponding boiling points of sample 5- are at least 1 C. higher and, therefore, unsatisfactory.'

is shown in Table 2.

' ent in each case to the extent of 50% of the oil.

,peror lower portion, as the case may be, were eliminated, samples 1 and also would be satis-' factory.-

In other words, samples 2, 3,-and 4 come within the preferred 5% to 90% and to 80% boiling ranges above specifically set forth.

Referring now to the results obtained upon polymerization, it is significant that the yield It is also significant that the softening point ,of resin drops off with samples 1 and 5, and that a v the color increases with both samples.

of the resin drops sharply with sample 1 and rises sharply wtih sample 5.

It is also significant that the solubility of the resin in 95% ethyl alcohol or in isoamyl alcholol increases with samples 1 and 5, even though withsamples 2 and 3 the solubility is slightly higher than with sample 5 alcohol.

The foregoing shows that the resin obtained upon polymerization of, crude fractions falling in the case of isoamyl within the preferred intermediate boilingranges is unique in physical characteristics, and this is'substantiated when this resin is incorporated in a varnish in accordance with this invention.

For instance, the resin produced from the samples 2, 3, and 4 is highly suitable for-varnish solubility in organic solvents such as in isoamyl alcohol increases. Such increase also increases compatibility with varnish oils as well "as improves the quality of the film formed by the varnish.

Care'is preferably taken not to employ excessive quantities of catalyst. For instance,

when using boron .trifluoride-diethyl ether complex, the percentage of catalyst. to the unsaturrates present in the oil might be held below, say 3% to reduce color, and under certain circumstances, it maybe preferred to maintain the percentage of catalyst below 2.5% or lower, to improve still further the color of the resin; 0n the other hand, large quantitiesof catalyst may be employed without departing-from the broad concept of the invention. Y

Since the unpolymerized starting material is subject to polymerization and oxidation on standing, I prefer to use freshly prepared starting material, or if the starting material has been standing some time, I prefer to distill it purposes, whereas the resin produced from sample 1 is less satisfactory because of its lower softening point and that from sample 5 is less satisfactory because it can be incorporated into varnish oils only with considerable difliculty Both should be excluded in order to secure a reasonably uniform product.

Samples 1 to 5-were polymerized under identical conditions, namely, the conditions particularly set forth in Example 1, except that the time of reaction was shortened to 6 hours.

Polymerization conditions, may be varied considerably in preparing the resins employed in the varnishes of this invention the phenols.

Attention is, however, directed to the effect of variation in concentration of catalyst. This In the experiments of Table 2, a typical sample of my starting material was employed. 'ill'iisv corresponded to'a mixture of samples 2 to 4 inclusive of Table 1, to the exclusion of samples 1 and 5. The diluent was benzene and was pres- The catalyst was boron trifluoride-diethyl ether complex. The softening points were determined by the A. S. T. M. ball and ring method.

All of the polymers were completely soluble in ether, acetone, toluene, and in high flash petroleum naphtha.

It will be noted that with increase in quantity of catalyst, the yield increases progressively toapproximately theoretical, the softening decreases", color tends to, increase, particularly with relatively large quantities of catalyst, and

prior to use.

Ingeneral, the effect of aging of the starting material prior. to polymerization is to increase the color, decrease the yield, and decrease the softening point, i t

The advantages of using freshly distilled start-- ing material is thus clearly evidenced.

I may wash the unpolymerized starting material with dilute aqueous alkali, such as a dilute solution of caustic soda, to insure the absence of or decreased concentration of compounds, such as sulfur compounds, peroxides, aldehydes and if the presence of phenols is notdesired also Washing with dilute lowed either by a water wash, or by dry or steam distillation, or any two or more of the foregoing to remove residual alkali,'as well as residual impurities.

Therefore, if a crude fraction derived from tar produced in the pyrolytic decomposition of petroleum oil, has my boiling range specifications but does not produce a polymer having the expected properties, I find it expedient to freshly distill the starting material before polymerization,

or to wash with dilute alkali or other reagent,

or both.

However, regardless of whether the starting material has been washed or freshly distilled,

samples boiling slightly below my preferred boilingrange produce polymers of lower softening point and of substantially greater color than sampies within my preferred boiling range.

- Furthermore, sample boiling slightly higher than my preferred boiling range produce polymers I which have substantially higher softening points the varnishes of this invention may be defined by and frequently substantially higher color, and

which are less readily incorporated in varnish oils.

By employing light oi1 fractions falling within I my preferred intermediate boiling" range, polymers of a relatively high degree of uniformity for commercial purposes may be produced.

x The unique character of the resins employed in their softening and solubilizing characteristics.

The softenin point after the removal of -un-' polymerized oil is approximately between C.

and C.,by the A. S. T. M. ball. and ring;

method. They are completely soluble in an equal part of ether, acetone, toluene or high flash naphtha, and have at-least a significant solubility in isoamyl alcohol;

alkali is preferably fol-- This type of resin is compatible with linseed oil andchina wood oil, and is highly suitable for varnish formulations in which these oils are employed.

For instance, this type of resin retards the sela tion of China wood'oil during the cooking process to an excellent degree.

Furthermore, the resulting varnish has veryare superior to the usual types of resins produced nish of almost any desired length may be obtained.

from cracked distiilates, or, for example, the cumar type resins, due to its excellent color stability. Even on extended exposure to light resins of this type show no pronounced tendency to after-color. I

This type of resin is further characterized by its light color and transparent nature; particularly when incorporated in a varnish.

When incorporated in standard varnishes the film is lightin color, has a very smooth finish, is substantially free from tackiness, and impart; a

pleasing sensation to the touch.

Satisfactory surface films may be produced by applying to surfaces generally, and ifl'etal surfaces such as tin and iron in particular, the varnishes of my invention, and then baking or air-drying the coating thus applied or permitting it to dry in any other atmosphere.

In the preparation of my new varnishes, the

I resin may be incorporated, in any suitable manner, into any drying oil employed in the oil varnish industry. Examples of such drying oils are Chinaans-as es Examples of drying oil varnishes prepared in accordance with my invention are as follows:

EXAMPLE 2 perature of 560 F. durinea period of 10 minutes and held at this temperature for an additional period of 3 minutes. It was permitted to cool to 535 F. and held at this temperature until the desired body was obtained, as measured by the length of, the s'tringspun from a cooled drop of the varnish mixture. ,The mixture then was chilled to 400 F. and reduced by the addition of 293.3

parts of mineral spirits. I

After reaching room temperature, 22.2 parts of a mixture of cobalt and manganese Oilsolates" (commercial driers which are salts of high molecular weight fatty acids) was added to the varnish. EXAMPLE 3 A mixture of 120 parts of processed oiticica oil and 100 parts of a resin prepared as'in Example land having a softening point of 80 C. was

heated to a temperature of 560 F. during a period of 30 minutes, after which it was held at this temperature until the desired body had been attached, after which it was cooled to 400 F. and reduced by the addition of 293 parts of mineral spirits. Upon reaching room temperature,

' the required drier (23 parts of cobalt and manwood oil (tung oil), oiticica oil, dehydrated castor oil, linseed oil, isomerized linseed oil, perilla oil, rapeseed oil, fish oil, sardine oil, menhaden oil, processed fish oils, soya bean oil, cottonseed oil, and the like. V

I have obtained varnishes exhibiting particuiarly desirable properties by the incorporation of the resin into China-wood oil, oiticica oil and 'iso-' merized linseed oil.

In most instances, it is desirable to incorporate a drier into my oil varnish mixture, Among the driers which may be employed are the lead, cobalt and manganese salts of high molecular weight organic acids such as naphthenic acid,,oleic acid, linoleic acid and the like.

The proportion of resin to drying oil employed I in the prp ration of varnishes in accordance with my invention maybe widely varied so that a verofavarnish is the, number of gallons of drying oil per'hundred pounds of resin.

ganese Oilsblates) was added.

- EXAMPLE 4 A mixture of 120 parts of 4 hour bodied linseed oil and 100 parts of a resin prepared as in Exampie 1 and having a softening point of C. was heated to a temperature of 585 F. during a period of 35 minut es. It was maintainedat this temperature until the desired body had been attained, after which it was cooled at 400 F. and

reduced bythe addition of 290 parts of mineral spirits. The drier of Example 2'was stirred in upon reaching room temperature.

/ EXAMPLE 5 Add 50 pounds of boiled linseed oil to chill the I have obtained highly desirablelvarnishes hav- .a ing lengths of 5 to gallons. In other words highly desirable varnishes may be prepared em-' ploying 5 to 100 sallonsof drying oil for each 100 pounds of mytype resin. A particularly desirable ,varnish is obtained when less than 30 gallons of drying oil are employed for each 100 pounds of my type resin,in other words, a varnish'havinga length of less than 30 gallons.

A preferred varnish has. a length of from 12 to .20 gallons, with 15 gallons or, in other words, 15 gallons oil to every 100 pounds of resin as a good all around example.

mix, removing the source of heat. After the temperature has fallen to about 400 F., thin with 475 pounds of mineral spirits. It may be desirable to add 5-10% of dipentene to the thinher to reduce skinning and wrinkling tendencies.

'6 Mix pounds of a resin prepared as in Example l and having a softening point less than 100 C. with 300 p unds of China-wood oil and heat from 350 to 560 F. in about 25 minutes.

Remove the-source of heat and chill the mixture with 1'15 pounds, of bodied linseed oil. After.

cooling thin with mineral spirits to 25-30% solids. The resins described herein when used in the 15 gallon varnishes of Examples 2, 3,'and 4, as

well as in varnishes generally, producebighly suitable results and are very acceptable to the trade.

varnishes made therefrom have excellent color stability.

The excellent exposure characteristics of -var-. nishes prepared from resins of the type described herein are shown by the following evaluation. Steel panels were thoroughly cleaned, given a round coat with a commercial undercoatin following varnishes:

1. -gallon varnish prepared in Example 2 Q 2.. 15-gallon modified phenolic resin-tung oil varm h v 3. 15-gallon ester gum-tung oil varnish 4. 15-gallon cumar-tung oil varnish 5. A commercial alkyd varnish 6. A commercial exterior spar varnish 7. A commercial modified phenolic varnish 8. A commercial phenolic varnish 9. A commercial ester gum varnish '10. A commercial rosin ester varnish The coated panels were exposed to the atmosphere in a highly industrialized locality at an anagle of 45 to the horizontal, facing south. The following coatings failed in the indicated periods of time.

1. No failure at the end of 28 weeks 2. 22 weeks 3. weeks 4.. 26 weeks 5. 20 weeks 6. 26 weeks 7. 16 weeks 8. 18 weeks 9. 16 weeks 10. 16 weeks;

- liquids (either catalyst or starting material) so that the other is relatively concentrated. It is' also possible with the exercise of extreme care and adherence to the principles set forth herein, to use both liquids in more concentrated form.

- composition, and then given two coats of the resin obtainable by the catalytic polymeriza- 20 boron trifluoride gas into this space in a manner to hold its concentration below say 2% when the boron trifluoride gas is diluted with another gas, such as ntirogen, and is introduced directly into the solution, it is alsogood practice to hold the concentration of boron trifluoride 0 gas in the gas mixture below say 2%.

Since the boron trifluoride gas is absorbed by the solution thefeedingfof gas, either into the space above .the solution or into the solution itself, is stopped after the desired quantity of catalyst has been absorbed.

Other variations are possible and will occur to personsskilled in the art upon familiar with this invention.

Broadly summarizing: this invention relates to dryingoil varnishes; and it comprises a drying oil varnish havingincorporated therein a tion of a more or less narrow crude fraction, ad-

vantageously having 5% and 90% boiling points betweenapproximately 167.2" C. and 174.6 C., separated from the hydrocarbon mixture obtained as the result of cracking oil in gas manufacture, advantageously in such proportions as to obtain a varnish of from 5 to 100 gallons in length and more preferably of less than 30 gallons in length; the invention further comprises objects coated with such vamishes all as more fully hereinabove set forth and as claimed.

While I have particularly described my invention it is to be understood that this is by way of illustration and that changes, omissions, ad-

ditiors, substitutions and/or modifications" might be madewithin the scope of the claims without departing from the spirit of the invention which is intended to be limited only as required by the prior art.

Iclaim: 1. A drying oil varnish having incorporated therein the resin resulting from the catalytic polymerization by means of a readily hydrolyzable metallic halide catalyst of a hydrocarbon fraction obtained from light oil produced during Other variations are possible. When adding one liquid -to another with agitation, I find 'it-convenient and often preferable to do this below the surface of one of the liquids.

Any other suitable alkali such as sodium hydroxide, sodium carbonate, sodium bicarbonate,

magnesium hydroxide, an amine or other basic substance might be substituted for quickiime in Example 1 followed by a non-acidic drying agentthe pyrolytic decomposition of petroleum oil for the manufacture of combustible gas" and free from substantial amounts of oxygen-containing compounds; said fraction having 5% and boiling points between approximately 167.2 C.

and 174.6 Clandcontaining a plurality of unsaturated'hydrocarbons, and said varnishzhaving a varnish length between 5 and gallons.

2.-A'drying oil varnish having incorporated f therein the resin resulting from the catalytic polymerization by means of a readily hydrolyzable metallichalide catalyst of a hydrocarbon fraction, obtained from lightoil produced during the pyrolytic decomposition of petroleum oil for such as sodium sulphate or soda lime. Both neutralizing and drying is effected by quickiime. Or the catalyst might be removed in any other manner. .1

When using boron trifluoride gas as a catalyst,

I prefer to employ a water jacketed closed kettle and to introduce the gas into the kettle either above the solution in a manner so that the gas .willbe present in low concentration, or to introduce the gas directly into the'solution but. in 1 diluted form. r

For instance, it the space above the solution is previously filled with air or with an inert gassuch as nitrogen, it'is good practice to introduce the manufacture of.-combustible gas and free from substantial amounts of oxygen-containing compounds: said fraction having 5% and 90% boiling points between. approximately 167.2 ,C. and 174.6 C. and containing a, plurality of unsaturated hydrocarbons, said varnish having a varnish length of more than 5 gallons and less than 100 gallons,'and said resin having a softening point of less than 100 C. i

- 3. A liquid coating composition comprising a drying oil and a resin resulting from the catalytic polymerization by means of a readily hy drolyzable metallic halide catalyst of a hydrocarbon fraction obtained from light oil produced during the 'pyrolytic decomposition of petroleum oil for the manufacture of combustible gas and free from substantial amounts'of oxygen-combecoming 90% boiling points between approximately 167.?

C. andl'ld.6 C. and containing a plurality of unsaturated hydrocarbons; the proportion of drying oil to resin being substantially between 5 and 30 gallons of drying oil per 100 pounds of resin.

4. A liquid coating composition. comprising China-wood oil and a resin resulting from the catalyst polymerization by means of an acid acting metallic halide catalyst of a hydroearbon fraction obtained from light oil produced during the pyrolytic decomposition of petroleum oil for the manufacture of combustible gas and free from substantial amounts of oxygen-containing compounds; said fraction having 5% and 90% boiling points between approximately 167.2 C. and 174.6? C., and containing a plurality of unsaturated hydrocarbons; the proportion of Chinaewood oil to resin being substantially between and 30 gallons of China-wood oil per 100 pounds" of resin.

5. A liquid. coating composition comprising oiticica oil and a resin resulting from the catalytic polymerization by means of an acid acting metallic halide catalyst of a hydrocarbon fraction obtained from light oil produced during the pyrolytic decomposition of petroleum oil for the manufacture of combustible gas and free from substantial amounts of oxygen-containing compounds; said fraction having 5% and 90% boiling points between approximately l67.2 C.

and 174.6 C. and containing a plurality of unsaturated hydrocarbons; the proportion of oiticica oil to resin being substantially between. 5 and 30 gallons of oiticica oil per 100 pounds of resin. V

6, A liquid coating composition comprising isomerized-linseed oil and a resin resulting from the catalytic polymerization by means of an acid acting metallic halide catalyst of a hydrocarbon fraction obtained from light oil produced during the pyrolytic decomposition of petroleum oil for the manufacture of combustible gas and free from substantial amounts-of oxygen-containing compounds; said fraction having 5% and. 90% boiling points between approximately 167.2 C. and 17%.6" C. and containing a plurality of unsaturated hydrocarbons; the proportion of isomerized linseed oil to resin being substantially between 5 and 30 gallons of isomerized linseed oil per 100 pounds of resin.

'7. A liquid coatingcomposition comprising, a drying oil and a resin having a softening point less than 100 C. and resulting from the catalytic polymerization by means of a readily hydrolyzable metallic halide catalyst of a hydrocarbon fraction obtained from light oil produced during the pyrolytic decomposition of petroleum oil for the ,manufacture of combustible gas and free from substantial amounts of oxygen-containing compounds; said fraction having 5% and 90% boiling points between approximately 167.2 C. and'174.6

C. andrcontaining aplurality of unsaturated hydrocarbons; the proportion of drying oil to resin being substantially between 12 and 20 gallons of drying oil er 100 pounds of resin.

81A liquid coatingcomposition comprising a drying oil and a resin having a softening point less than 100 C. and resulting'from the catalytic polymerization bymeans of a readily hydrolyzable metallic-halide catalyst of a hydrocarbon fraction obtained from light oil produced during the pyrolytic decomposit on of petroleum oil for, the manufacture of combustible gas and free from I vsubstantial amounts of oxygen-contain ng compounds; said fraction having 5% and 90% boiling points between approximately 167.2 C. and 174.6

- (3., and containing a plurality of unsaturated hydrocarbons; the proportion of drying oil to resin 5 being approximately equivalent to 15 gallons of drying oil to 100 pounds of resin.

9. A drying oil varnish having incorporated therein a resin obtained by a process comprising catalytically polymerizing a hydrocarbon fraction obtained from light oil produced during the pyrolytic decomposition of petroleum oil for the manufacture of combustible gas and free from sub 7 stantial amounts of oxygen-containing compounds, said fraction having 5% and 90% boiling points between approximately 167.2" C. and 17%.5" C. and containing a plurality of unsaturated hydrocarbons, by contacting said fraction with a readily hydrolyzable metallic halide catalyst to catalyze the formation of polymer, said varnish having a varnish length of between 5 and 20 gallons.

10. A. drying oil varnish having incorporated therein a resin obtained by a process comprisin catalytically polymerizing a hydrocarbon fraction obtained from light oil produced during the pyro lytic decomposition of petroleum oil for the mantle facture of combustible gas and free'from sub-' stantial amounts or oxygen-containing compounds, said fraction having 10% and 80% boiling points between approximately 167.4" C. and 173.2" (3. and containing a plurality of unsa rated hydrocarbons, by contacting said fraction with a readily hydrolyzable boron trifiuorideorganic solvent complex to catalyze the forma- 85 tionof polymer, said catalyst complex resulting from the admixture of boron trifiuoride with an organic solvent capable of reacting therewith to form said complex, said varnish having a varnish length of between 5 and gallons.

11. A drying oil varnish having incorporated therein a resin obtained by a process comprising catalytically polymerizing a hydrocarbon fraction obtained from light oil produced during the py olytic decomposition of petroleum oil for the manu- 5 facture of combustible-gas and free from substan tial amounts of oxygen-containing compounds, said fraction having 10% and 80% boiling points between approximately 167.4 C. and 173.2 C. and containing a plurality of unsaturated hydrocarbons, by contacting said fraction with a readily hydrolyzable aluminum chloride-organic solvent complex tocatalyze the formation of polymer, said catalyst complex resulting from the admix-. ture of aluminum chloride with an organic solvent capable of reacting therewith to form said complex, the proportion'of drying oil to resin in said varnish being substantiallyequivalent to approximately '12 to 20 gallons of drying oil per 100 pounds of resin.

12. The method of making a liquid coating composition which comprises heating a drying oil with a resin obtained by a process comprising catalytically polymerizing a hydrocarbon fraction obtalned from light oil'produced during the pyrolytic decompositione'of petroleum oil for the manufacture of combustible igas and free from substantial amounts of oxygen containing compounds. said fraction having 5% and 90% boiling points. between approximately 167.2" Cjand 174.6" C. and ontaining a plurality of unsaturated hydrocar bons. bv contacting said fraction with a readily 'nvdrolyzable metallic halide catalyst to catalyze the formation of polymer, the Proportion Dffll'Y'. inc oil to resin in said liquid coating composition being substantially equivalent to between 5 and 13. A dryins oil comprising china-wood oil and a resin produced. by a process comprising cata lytically polymerizing a hydrocarbon fraction obtained' from light oil' produced during the pyrolytic decomposition of petroleum oil for the-manufacture of combustible gas and free from substantial amounts of oxygen-containing compounds,-

sald fraction having 10% and 80% boiling points between approximately 167,4 0. and 173.2 C. and

Y complex to catalyze the formation of polymer,

hydrolymhlo sluininuni-chloride organic solvent said catalyst complex resulting from the admixcontaining a plurality of unsaturated hydrocarbons by contacting said -fraction with a readily ture of aluminum chloride with an ,oranic solvent 'capable of reacting therewith to form said complex, the proportion of China-wood oil to resin in said varnish being approximately equivalent to 15 gallons of China-wood oil per 100 pounds of resin.

' 14. A drying oil varnish according to claim 1 'in which the light oil ,fraction-polymeri'zed to pro duce the resin is a freshly distilled traction.

AIGERL. WARD. 

